Polyol or polythiol compound, preparation method therefor, transparent polyurethane-based resin prepared therefrom, and optical body

ABSTRACT

The present invention relates to a novel polyol or polythiol having three or more functional groups, a preparation method there for, and an optical body manufactured therefrom. Especially, the present invention relates to a poly(thio)urethane-based resin and an optical body, such as lenses, manufactured using the resin, wherein the poly(thio)urethane-based resin is prepared by obtaining a novel polyol and then combining a polythiol, which is prepared from the obtained polyol, with a polyiso(thio)cyanate.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a national stage application, filed under 35 U.S.C.§ 371, of International Patent Application No. PCT/KR2018/001884, filedon Feb. 13, 2018, which is incorporated by reference herein in itsentirety.

TECHNICAL FIELD

The present invention relates to a novel polyolorpolythiol, a method ofpreparing the same, and a polyurethane resin prepared therefrom. Inparticular, the present invention relates to an optical bodyformed of apoly(thio)urethane resin prepared by reacting a novel polythiol with apolyiso(thio)cyanate compound.

BACKGROUND ART

In recent years, resins for plastic lenses are required to have furtherimproved performance together with high refractivity, high Abbe'snumber, low specific gravity, high heat resistance, and the like.Currently, various resins for plastic lenses have been developed andused in the art. In particular, a poly(thio)urethane resin generallyused for plastic lenses is recently applied to optical devices includingeyeglass lenses, camera lenses, and the like.

The poly(thio)urethane resin is obtained by reacting a polythiol with apolyiso(thio)cyanate compound. The polythiol or a polyol as anintermediate compound thereof is broadly used for various applicationsas a raw material for optical bodies, poly(thio)urethane resins orsynthetic resins, a crosslinking agent, an epoxy resin curing agent, avulcanizing agent, a polymerization regulator, a metal complex, and abiochemical lubrication additive.

Although various functions may be provided to the poly(thio)urethaneresin for lenses and optical bodies through modification of apolyiso(thio)cyanate compound used as a component of thepoly(thio)urethane resin, there is a problem of limitation in kindthereof. Accordingly, the polythiol used as another component thereofmay be modified to provide various functions to the poly(thio)urethaneresin and there is a need for various polythiols.

A method of preparing such a polythiol is disclosed in various documentsin the art, for example, Patent Documents 1 to 3. Patent Document 1discloses a method of preparing a polythiol compound, in which thecontent of a certain additive present in 2-mercapto ethanol isrestricted to within a predetermined range.

Patent Document 2 discloses a method in which the content of calciumpresent in thiourea is restricted to within a predetermined range.Patent Document 3 relates to a polythiol composition and use thereof,and discloses a polythiol compound having at least three mercapto groupsand a polythiol composition comprising a small amount of anitrogen-containing compound in which one mercapto group of thepolythiol compound is substituted with a hydroxyl group. All of PatentDocuments 1, 2 and 3 disclose the method of preparing a polythiolcompound using 2-mercapto ethanol. In particular, Patent Document 2discloses a general method for preparing a polythiol compound byreacting 2-mercapto ethanol with an epihalohydrin compound. Currently,the preparation of 2-mercaptoethanol restrictively starts from ethyleneoxide.

On the other hand, Patent Document 4 was filed based on Korean PatentApplication No. 10-2017-0020263 (Application Date: 2017 Feb. 15) andpublished on Jul. 7, 2017. This document discloses a polythiol compoundprepared by preparing 1-mercapto-2-propanol from propylene oxide,followed by reacting with epichlorohydrin. However, the invention ofthis patent document has various problems in that preparation of adesired polythiol compound cannot be secured in an example disclosingthat a polythiol intermediate compound was prepared from a polyolintermediate compound.

PRIOR LITERATURE Patent Document

(Patent Document 1) International Publication No. WO 2007/129449

(Patent Document 2) International Publication No. WO 2007/129450

(Patent Document 3) International Publication No. WO 2014/027665

(Patent Document 4) Korean Patent Laid-openPublication No.10-2017-0078139

DISCLOSURE Technical Problem

For a poly(thio)urethane resin reported in the related art, it isdifficult to manufacture an optical lens satisfying dyeing propertieswhile maintaining high heat resistance. The dyeing properties refer tophysical properties of a transparent resin prepared through reaction ofa polythiol with a polyiso(thio)cyanate compound. The dyeing propertiesof a certain resin are obtained by dyeing the resin for shieldingvisible light. In general, increase in heat resistance of a resinresults in reduction in dyeing properties thereof and increase in dyeingproperties of the resin results in reduction in heat resistance thereof.Therefore, there is a need for a polythiol capable of satisfying bothhigh heat resistance and high dyeing properties of a transparent resinprepared from a poly(thio)urethane composition.

The inventors of the present invention have conducted various andintensive studies to develop a polythiol satisfying such requirements.As a result, it was found that heat resistance of a transparent resincan be improved by regulating the volume and size of side chains whilemaintaining the same structure in molecules among factors affecting theglass transition temperature (Tg) of the transparent resin. Based onthis finding that heat resistance of the transparent resin can beimproved while maintaining the dyeing properties thereof, the inventorsinvented a novel polythiol through modification of a molecular structureof a polythiol.

The present invention is aimed at providing a polyol or polythiolcompound, which is prepared using a starting material instead of2-mercapto ethanol used in the art and can secure high heat resistanceof a transparent lens formed thereof while allowing easy coloration andgood dyeing properties of the transparent lens, and a method ofpreparing the same. In addition, the present invention is aimed atproviding an optical body formed of a poly(thio)urethane resin preparedby reacting a novel polythiol with apolyiso(thio)cyanate compound.

Technical Solution

One aspect of the present invention relates to a polyol or polythiolcompound or an isomer thereof, the polyol or polythiol compound havingat least three functional groups and represented by Formula (a) or (b):

(where Y is an oxygen atom or a sulfur atom;

Ra is a lower alkyl group,

i) for the polyol, Rb is —CH₂CH(OH)CH₂F, —CH₂CH(OH)CH₂Cl,—CH₂CH(OH)CH₂Br, —CH₂CH(OH)CH₂I,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₃,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₃)CH₂OH,

—CH₂CH(OH)CH₂OH, —CH₂CH(OH)CH₂SCH₂CH(OH)CH₃, —CH₂CH(OH)CH₂SCH(CH₃)CH₂OH,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃, —CH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH_(b), or

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH;

ii) for the polythiol, Rb is —CH(CH₂SH)CH₂SH, —CH₂CH(CH₂SH)SH,

—CH₂CH(CH₂SH)SCH(CH₃)CH₂SH, —CH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₃)CH₂SH, —CH(CH₂SH)CH₂SCH₂CH(CH₃)SH,

—CH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH, —CH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, —CH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₂)CH₂SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₃) SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₂)CH₂SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, or

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH).

In Formula (a) or (b), Y may be an oxygen atom; Ra may be a methyl orethyl group, and Rb may be one substituent selected from the groupconsisting of the following substituents:

—CH₂CH(OH)CH₂F, —CH₂CH(OH)CH₂Cl, —CH₂CH(OH)CH₂Br, —CH₂CH(OH)CH₂I,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₃,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₃)CH₂OH,

—CH₂CH(OH)CH2OH,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₃,

—CH₂CH(OH)CH₂SCH(CH₃)CH₂OH,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃,

—CH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH,

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃, and

—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH.

In addition, in Formula (a) or (b), Y may be a sulfur atom; Ra may be amethyl or ethyl group; and Rb may be one substituent selected from thegroup consisting of the following substituents:

—CH(CH₂SH)CH₂SH, —CH₂CH(CH₂SH)SH, —CH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₃)SH, —CH(CH₂SH)CH₂SCH(CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₃)SH, —CH₂CH(CH₂SH)SCH(CH₂CH₃) CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH, —CH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂CH₃₎SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, and

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH.

Another aspect of the present invention relates to a method of preparinga polythiol represented by Formula (1) or an isomer thereof according toReaction Scheme 1, the method comprising the steps of:

(1) preparing an intermediate compound of Formula (5) by reacting amercapto compound of Formula (2) with an epihalohydrin compound ofFormula (4) in an equivalent ratio of 1:1;

(2) preparing a polyol compound of Formula (6) by adding an aqueoussodium sulfate solution to the prepared intermediate compound of Formula(5) and by reacting them; and

(3) adding an inorganic acid and thiourea to the prepared polyolcompound of Formula (6), heating, stirring and cooling a mixture of theinorganic acid, thiourea and the polyol compound to room temperature,followed by adding a basic aqueous solution to a resulting product tohydrolyze the resulting product:

(where

X is one selected from the group consisting of F, Cl, Br and I,

R1′ is one selected from the group consisting of —CH₂CH(OH)CH₂F,—CH₂CH(OH)CH₂Cl, —CH₂CH(OH)CH₂Br, and —CH₂CH(OH)CH₂I,

R1″ is —CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₃ or—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₃)CH₂OH, and

R3 is one selected from the group consisting of—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH, and

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH).

A further aspect of the present invention relates to a method ofpreparing a polythiol represented by Formula (1) or an isomer thereofaccording to Reaction Scheme 2, the method comprising the steps of:

(1) preparing an intermediate compound of Formula (7) by reacting 1equivalent weight of a mercapto compound of Formula (3) with 1equivalent weight of an epihalohydrin compound of Formula (4);

(2) preparing a polyol compound of Formula (8) by adding an aqueoussodium sulfate solution to the prepared intermediate compound of Formula(7) and by reacting them; and

(3) adding an inorganic acid and thiourea to the prepared polyolcompound of Formula (8), heating, stirring and cooling a mixture of theinorganic acid, thiourea and the polyol compound to room temperature,followed by adding a basic aqueous solution to a resulting product tohydrolyze the resulting product:

(where

X is one selected from the group consisting of F, Cl, Br and I,

R2′ is one selected from the group consisting of —CH₂CH(OH)CH₂F,—CH₂CH(OH)CH₂Cl, —CH₂CH(OH)CH₂Br, and —CH₂CH(OH)CH₂I,

R2″ is —CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₃ or—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₃)CH₂OH,

R3 is one selected from the group consisting of

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₃₎SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₃) SH,

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH, and

—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH).

Yet another aspect of the present invention relates to a method ofpreparing a polythiol represented by Formula (1) or an isomer thereofaccording to Reaction Scheme 3, the method comprising the steps of:

(1) preparing a polyol compound of Formula (5) or (7) by reacting amercapto compound of Formula (2) or (3) with a glycidol compound in anequivalent ratio of 1:1; and

(2) adding an inorganic acid and thiourea to the prepared polyolcompound of Formula (5) or (7), heating, stirring and cooling a mixtureof the inorganic acid, thiourea and the polyol to room temperature,followed by adding a basic aqueous solution to a resulting product tohydrolyze the resulting product:

(where R1′ and R2′ are each —CH₂CH(OH)CH₂OH and R3 is —CH(CH₂SH)CH₂SH or—CH₂CH(CH₂SH)SH).

Yet another aspect of the present invention relates to a method ofpreparing a polythiol represented by Formula (1) or an isomer thereofaccording to Reaction Scheme 4, the method comprising the steps of:

(1) preparing a polyol compound of Formula (5) or (7) by reacting amercapto compound of Formula (2) or (3) with an epihalohydrin compoundof Formula (4) in an equivalent ratio of 2:1; and

(2) adding an inorganic acid and thiourea to the prepared polyolcompound of Formula (5) or (7), heating, stirring and cooling a mixtureof the inorganic acid, thiourea and the polyol to room temperature,followed by adding a basic aqueous solution to a resulting product tohydrolyze the resulting product:

(where X is one selected from the group consisting of F, Cl, Br and I,

R1′ and R2′ are each —CH₂CH(OH)CH₂SCH₂CH(OH)CH₃ or—CH₂CH(OH)CH₂SCH(CH₃)CH₂OH, and

R3 is —CH₂CH(CH₂SH)SCH₂CH(CH₃)SH, —CH₂CH(CH₂SH)SCH(CH₃)CH₂SH,

—CH(CH₂SH)CH₂SCH₂CH(CH₃)SH, or —CH(CH₂SH)CH₂SCH(CH₃)CH₂SH).

Yet another aspect of the present invention relates to a method ofpreparing a polythiol represented by Formula (11) according to ReactionScheme 5, the method comprising the steps of:

(1) preparing an intermediate compound of Formula (15) by reacting amercapto compound of Formula (12) with an epihalohydrin compound ofFormula (4) in an equivalent ratio of 1:1;

(2) preparing a polyol compound of Formula (16) by adding an aqueoussodium sulfate solution to the prepared intermediate compound of Formula(15) and by reacting them; and

(3) adding an inorganic acid and thiourea to the prepared polyolcompound of Formula (16), heating, stirring and cooling a mixture of theinorganic acid, thiourea and the polyol compound to room temperature,followed by adding a basic aqueous solution to a resulting product tohydrolyze the resulting product:

(where X and R1′ are the same as each substituent of Reaction Scheme 1,

R1″ is —CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃,

R3 is one selected from the group consisting of—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃₎SH,

—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃₎SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, and—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH).

Yet another aspect of the present invention relates to a method ofpreparing a polythiol represented by Formula (11) or an isomer thereofaccording to Reaction Scheme 6, the method comprising the steps of:

(1) preparing a polyol compound of Formula (15) by reacting a mercaptocompound of Formula (12) with an epihalohydrin compound of Formula (4)in an equivalent ratio of 2:1; and

(2) adding an inorganic acid and thiourea to the prepared polyolcompound of Formula (15), heating, stirring and cooling a mixture of theinorganic acid, thiourea and the polyol to room temperature, followed byadding a basic aqueous solution to a resulting product to hydrolyze theresulting product:

(where

X is one selected from the group consisting of F, Cl, Br and I,

R1′ is CH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃,

R3 is —CH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH, —CH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, or —CH(CH₂SH)CH₂SCH₂CH(CH₂CH₃) SH).

In the method of preparing the polythiol represented by Formula (1), TEAor NaOH may be used as a catalyst. Further, in the method of preparingthe polythiol represented by Formula (1), the inorganic acid may behydrochloric acid, nitric acid, sulfuric acid, or hydrobromic acid.Furthermore, the basic aqueous solution may bean aqueous ammoniasolution, an aqueous sodium hydroxide solution, an aqueous lithiumhydroxide solution, or hydrazine.

The alcohol intermediate compound of Formula (5), (7) or (15) isprepared by reacting, as a starting material, about 2 or more equivalentweights of a mercapto-ethyl alcohol substituted with a lower alkylgroup, such as the compound of Formula (2) or (3) in Reaction Scheme 4or the compound of Formula (12) in Reaction Scheme 6, with 1 equivalentweight of the epichlorohydrin compound of Formula (4), and has asymmetrical structure.

In addition, the halo-alcohol intermediate compound of Formula (5), (7)or (15) is prepared by reacting, as a starting material, about 1equivalent weight of a mercaptoethyl alcohol substituted with a loweralkyl group, such as the compound of Formula (2) in Reaction Scheme 1,the compound of Formula (3) in Reaction Scheme 2, or the compound ofFormula (12) in Reaction Scheme 5, with 1 equivalent weight of theepichlorohydrin compound of Formula (4).

The polyol intermediate compound of Formula (6), (8) or (16) is preparedby reacting about 1 equivalent weight of the compound of Formula (5) inReaction Scheme 1, the compound of Formula (7) in Reaction Scheme 2, orthe compound of Formula (15) in Reaction Scheme 5 with 0.5 equivalentweight of Na₂S, and has a symmetrical structure.

As mentioned in the background technique, in Preparation Example (1) andComparative Example (1) of Patent Document 4 (KR Patent Laid-openPublication No. 10-2017-0078139), an epichlorohydrin or epoxy compoundsubstituted with a halo-alkyl group is reacted with a mercaptoethylalcohol or a mercaptoethyl alcohol substituted with a lower alkyl group.However, since a polyol intermediate compound prepared by this reactionhas an asymmetrical structure, a polythiol cannot be prepared from sucha polyol intermediate compound or through such an asymmetrical polyolintermediate compound, in light of Reaction Formulas 1 to 6.

Yet another aspect of the present invention relates to a polyol compoundas an intermediate compound of the polythiol compound, which may beprepared by the method of preparing the polyol of Formula (6) or (8),which includes Steps (1) and (2), in Reaction Scheme 1 or 2. Inaddition, another polyol compound may be prepared by the method ofpreparing the polyol of Formula (7), which includes Step (1), inReaction Scheme 3 or 4. As in the method of preparing a polythiol, themethod of preparing the polyol compound as an intermediate compound mayemploy TEA or NaOH as a catalyst.

Yet another aspect of the present invention relates to apoly(thio)urethane resin composition comprising the polythiol having atleast three functional groups, which is prepared by one of the methodsdescribed above, and a polyisocyanate. Here, a mole ratio (═NCO/SH) of afunctional group (—NCO) of the polyisocyanate to a functional group(—SH) of the polythiol compound ranges from 0.6 to 2.0, preferably from0.8 to 1.3, more preferably from 0.9 to 1.1. Within this range, thepoly(thio)urethane resin composition can secure balance between variousfunctions including refractivity, heat resistance, and the like, whichare required for an optical material and a transparent material forplastic lenses.

Yet another aspect of the present invention relates to apoly(thio)urethane resin formed by heating and curing thepoly(thio)urethane resin composition. Furthermore, yet another aspect ofthe present invention relates to a poly(thio)urethane plastic opticalbody manufactured by a method of preparing a poly(thio)urethane plasticlens, which includes polymerizing the poly(thio)urethane resincomposition in a mold and releasing a molded product from the mold.Here, a mole ratio (═NCO/SH) of a functional group (—NCO) of thepolyisocyanate to a functional group (—SH) of the polythiol compoundranges from 0.6 to 2.0, preferably from 0.8 to 1.3, more preferably from0.9 to 1.1.

Although the plastic optical body of the present invention may beapplied not only to an optical lens, but also to large-area windows,such as sliding windows, single or double hung windows, side-hingedwindows, and the like, which are used in buildings and the like, aplastic optical lens will be mainly described as one example of theplastic optical body in the following description.

DESCRIPTION OF DRAWINGS

FIG. 1 shows ¹H-NMR spectrum of Example 1 (Compound 1) according to thepresent invention.

FIG. 2 shows ¹H-NMR spectrum of Example 3 (Compound 3) according to thepresent invention.

FIG. 3 shows ¹H-NMR spectrum of Example 4 (Compound 4) according to thepresent invention.

FIG. 4 shows ¹H-NMR spectrum of Example 5 (Compound 5) according to thepresent invention.

FIG. 5 shows ¹H-NMR spectrum of Example 7 (Compound 7) according to thepresent invention.

FIG. 6 shows ¹H-NMR spectrum of Example 8 (Compound 8) according to thepresent invention.

FIG. 7 shows ¹H-NMR spectrum of Example 9 (Compound 9) according to thepresent invention.

FIG. 8 shows ¹H-NMR spectrum of Example 10 (a mixture of Compounds 10-1to 10-4, GPT) according to the present invention.

FIG. 9 shows ¹H-NMR spectrum of Example 11 (a mixture of Compounds 11-1to 11-4, MPT) according to the present invention.

FIG. 10 shows ¹H-NMR spectrum of Example 12 (a mixture of Compounds 12-1to 12-10, BPT) according to the present invention.

FIG. 11 shows ¹H-NMR spectrum of Example 13 (a mixture of Compounds 13-1to 13-10, BBT) according to the present invention.

FIG. 12 shows ¹H-NMR spectrum of Example 14 (a mixture of Compounds 14-1to 14-4, BBT) according to the present invention.

BEST MODE

Hereinafter, embodiments of the present invention will be described indetail with reference to the accompanying drawings.

Among mechanical properties of a lens produced from a polyurethaneresin, heat resistance of the lens is related to the glass transitiontemperature Tg of the polyurethane resin, which has a correlation withdyeing properties thereof related to color uniformity. Accordingly,increase in glass transition temperature Tg tends to deteriorate thedyeing properties. In general, a chemical structure affecting a glasstransition temperature Tg of a polymer compound may be examined from thepoint of view of flexibility of a main chain and flexibility of a sidechain. In comparison of flexibility of main chains, a main chain havinga benzene ring therein has lower flexibility of a main chain having nobenzene ring and increases the glass transition temperature Tg. Incomparison of flexibility of side chains, a side chain having a bulkfunctional group causing steric hindrance has low flexibility due todeterioration in rotatability, thereby causing increase in glasstransition temperature Tg. Polyethylene and polypropylene may be recitedby way of example. As a result, it can be confirmed that a polymercontaining polypropylene glycol has a higher glass transitiontemperature Tg than a polymer containing polyethylene glycol.

Based on this fact, the inventors of the present invention attempted tosynthesize a novel polythiol using propylene oxide or butylene oxide asa starting material for preparation of 2-mercapto ethanol, instead ofethylene oxide used in the art. In this case, a unit molecule fromethylene oxide (C-2) to propylene oxide (C-3), butylene oxide (C-4), andthe like was changed while maintaining the same structure sequence inthe molecule. Then, it was anticipated that, when the number of hydrogenatoms of an ethyl group increases due to a methyl molecule, the glasstransition temperature Tg would increase due to influence of sidechains, thereby completing the present invention.

According to the present invention, a polyol or polythiol compoundhaving at least three functional groups and represented by Formula (a)or (b) may be prepared by a process according to Reaction Formulas 1 to6.

Herein, unless specifically stated otherwise, a ‘halogen’ represented by‘X’ refers to fluorine, chlorine, bromine, or iodine, preferablychlorine.

Herein, a ‘lower alkyl group’ refers to a linear or branched alkyl grouphaving 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, morepreferably 1 to 4 carbon atoms. Specifically, the lower alkyl group maybe a methyl group, an ethyl group, an n-propyl group, an n-butyl group,an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octylgroup, an isopropyl group, an isobutyl group, a sec-butyl group, atert-butyl group, an isopentyl group, or the like, preferably a methylgroup or an ethyl group.

Polyol Compounds 1 to 9 represented by Formula (a) or (b) where Y is anoxygen atom, Ra is a methyl group or an ethyl group, and Rb is onesubstituent selected from the group consisting of the afore mentionedsubstituents may have the following structures and are named as follows.

Compound No. Structural Formula Compound Name 1

1-chloro-3-((2- hydroxypropyl)thio)propane-2-ol 2

2-((3-chloro-2- hydroxypropyl)thio)-propane-1-ol 3

3-((2- hydroxypropyl)thio)propane-1,2- diol 4

1,3-bis[2- hydroxypropyl)thio]propane-2-ol 5

bis[3-((2-hydroxypropyl)thio)- 2-hydroxypropyl]sulfide 6

bis[3-((1-hydroxy-propane-2- yl)thio)-2- hydroxypropyl]sulfide 7

1-((3-chloro-2- hydroxypropyl)thio)butane-2-ol 8

bis[3-((2-hydroxybutyl)thio)-2- hydroxypropyl]sulfide 9

1,3-bis[2- hydroxybutyl)thio]propane-2-ol

Further, among compounds represented by Formula (a) or (b) where Y is asulfur atom, Ra is a methyl group or an ethyl group, and Rb is oneselected from the group consisting of the aforementioned substituents,Polythiol Compounds 10 to 14 having the following structures and eachhaving isomers as follows are obtained.

In preparation of the polythiol compounds, it could be confirmed that anintermediate compound could be produced through rearrangement resultingfrom steric hindrance upon preparation of a sulfide intermediatecompound through reaction of each of the polyol intermediate compoundsmentioned above with the thiourea/hydrochloric acid. Upon hydrolysis ofthe intermediate compound, a primary polythiol may be obtained as aresulting compound. As a result of structural analysis of a polythiol tobe prepared by the method according to the present invention, it couldbe confirmed that the primary thiol compound is produced as a mainproduct together with a secondary polythiol. As a result, it can beconfirmed that a polythiol composition to be prepared by the methodaccording to the present invention consists of a mixture of isomers. Thefollowing table shows theoretically producible isomers.

(1) Isomers of Compound 10(GPT) and Compound 11(MPT)

Compound No. Structural Formula Compound Name Acronym 10-1

2-((1-mercaptopropan-2-yl) thio)propane-1,3-dithiol GPT 10-2

2-((2-mercaptopropyl)thio) propane-1,3-dithiol 10-3

3-((2-mercaptopropyl)thio) propane-1,2-dithiol 10-4

3-((1-mercaptopropan-2-yl) thio)propane-1,2-dithiol 11-1

3-((1-mercaptopropan-2-yl) thio)-2-((1-mercaptopropan-2-yl)thio)propane-1-thiol MPT 11-2

3-((1-mercaptopropan-2-yl) thio)-2-((2-mercaptopropyl)thio)propane-1-thiol 11-3

2-((1-mercaptopropan-2-yl) thio)-3-((2-mercaptopropyl)thio)propane-1-thiol 11-4

2-((2-mercaptopropyl)thio)- 3-((2-mercaptopropyl)thio) propane-1-thiol

(2) Isomers of Compound 12 (BPT)

Compound No. Structural Formula 12-1 

12-2 

12-3 

12-4 

12-5 

12-6 

12-7 

12-8 

12-9 

12-10

General names of representative Compounds 12-1 to 12-3 are as followsand names of other compounds are omitted:

-   -   Compound 12-1:        3,3′-thiobis(2-(1-mercaptopropan-2-yl)thio)-1-propanethiol;    -   Compound 12-2:        2-((3-mercapto-2-((1-mercaptopropan-2-yl)thio)propyl)thio)-3-((1-mercaptopropan-2-yl)thio)propane-1-thiol;        and    -   Compound 12-3:        2,2′-thiobis(3-(1-mercaptopropan-2-yl)thio)-1-propanethiol

(3) Isomers of Compound 13(BBT) and Compound 14(MBT)

Although Compound 13(BBT) may have 10 isomers, Compounds 13-1, 13-2 and13-3 are illustrated as representative isomers thereof, and althoughCompound 14(MBT) may have four isomers, Compounds 14-1 and 14-2 areillustrated as representative isomers thereof.

Compound No. Structural Formula Compound Name Acronym 13-1

2,2′-((thiobis(1-mercaptopropane- 3,2-diyl))bis(sulfanediyl)bis(butane-1-thiol) BBT 13-2

2,2′-((thiobis(3-mercaptopropane- 2,1-diyl))bis(sulfanediyl)bis(butane-1-thiol) 13-3

2-((3-mercapto-2-((3-mercapto- 2-((1-mercaptobutan-2-yl)thio)propyl)thio)propyl)thio)butane- 1-thiol 14-1

3-((1-mercaptobutan-2-yl)thio)- 2-((1-mercaptobutan-2-yl)thio)propane-1-thiol MBT 14-2

2-((2-mercaptobutyl)thio)-3- ((2-mercaptobutyl)thio)propane- 1-thiol

Next, a method of preparing Polyol Compounds 1 to 9 will be describedand a method of preparing Polythiol Compounds 10 to 16 the preparedpolyol compounds will be described.

(Polyol Preparation Method)

As shown in Reaction Formulas 1 to 6, the polyol compound according tothe present invention may be prepared by reacting an epihalohydrincompound or a glycidol compound with a mercapto compound as anintermediate compound of a polythiolin an equivalent ratio of 1:1 or inan equivalent ratio of 2:1, as described above.

The epihalohydrin compound may be represented by Formula 4 (where X is ahalogen atom) and may be obtained from commercially available products:

In addition, the glycidol compound (glycide; hydroxymethyl ethyleneoxide) may be represented by the following formula and may be obtainedfrom commercially available products:

Obviously, such a glycidol compound may be prepared by reacting benzoylperoxide with allyl alcohol or by heating epichlorohydrin together withpotassium acetic anhydride to prepare acetate and treating the preparedacetate with sodium hydroxide in ether by a method known in the art.

Synthesis reaction of the polyol may be performed at a temperature of10° C. to 50° C., preferably 20° C. to 30° C. If the reaction isperformed at a lower temperature than 10° C., low reaction conversioncan occur due to decrease in reaction rate. If the reaction is performedat a higher temperature than 50° C., the compound of Formula (2), (3) or(12) reacting with epichlorohydrin in the Reaction Formulas can beproduced together with an impurity or a dimer. In addition, the compoundof Formula (2), (3) or (12) used as a starting material of the mercaptocompound may be added for 0.5 to 10 hours, preferably 1 to 2 hours. Ifthe starting material is added for less than 0.5 hours, control of thereaction rate can be difficult and the compound of Formula (2), (3) and(12) can be produced together with an impurity or a dimer. The reactiontemperature and the reaction time may be suitably regulated within theabove ranges depending upon properties of each reactant and a solvent tobe used.

For Compounds 1, 2, 3 and 7, each of the compounds of Formulas (2), (3)and (12) may be used in an amount of 1 mole, preferably 0.9 moles to 1.1moles, with respect to 1 mole of epihalohydrin. If the compound is usedin an amount of less than 0.9, unreacted epihalohydrincan remain as animpurity affecting subsequent reaction. If the compound is used in anamount of greater than 1.1 mole, unreacted 2-mercaptopropanol reactswith a reaction product to produce an impurity having a symmetricalstructure wherein 2-mercaptopropanol is coupled to both sides ofepihalohydrin. However, for Compounds 4 and 9, each of the compounds ofFormulas (2), (3) and (12) may be used in an amount of 2 moles,preferably 2 moles to 3 moles, with respect to 1 mole of epihalohydrin.If the compound is used in an amount of less than 2 moles, an impurityhaving an asymmetrical structure can be produced through reaction of 1mole of 2-mercaptopropanol and 1 mole of epihalohydrin and can affectsubsequent reaction. If the compound is used in an amount of greaterthan 3 moles, an unreacted compound of Formula (2), (3) and (12) canremain and affects the subsequent reaction. Although Compounds 5, 6, and8 may be prepared by the above method, each of the compounds of Formulas(2), (3) and (12) may be used in a similar equivalent weight in order tosuppress generation of an impurity.

(Polythiol Preparation Method)

A sodium halogenide is additionally added to the prepared polyolcompound and an inorganic acid and thiourea are added to the mixture,followed by heating, stirring and cooling the mixture to roomtemperature. Then, a basic aqueous solution is applied to the mixture toproduce a polythiol compound through hydrolysis of the mixture. Theprepared polythiol compound may be subjected to a work-up process suchas solvent removal, filtration, vaporization, purification, and thelike.

As used herein, the inorganic acid may be selected from amonghydrochloric acid, nitric acid, sulfuric acid, hydrobromic acid, and thelike. When used as the inorganic acid, hydrobromic acid may be used inan amount of 3 to 5 moles with respect to 1 mole of the polyol compound.Here, reaction may be performed at a temperature of 100° C. to 105° C.If the reaction is performed at a temperature of less than 100° C., thereaction rate can significantly decrease. The reaction may be performedfor 3 hours to 8 hours and a reaction finish time may be confirmed basedon whether the polyol compound is completely consumed. As the inorganicacid, the hydrochloric acid may be used in an amount of 3 to 5 moleswith respect to 1 mole of the polyol compound. Here, reaction may beperformed at a temperature of 105° C. to 110° C. The reaction may beperformed for 12 hours to 24 hours and a reaction finish time may beconfirmed based on whether the polyol compound is completely consumed.

As used for hydrolysis, the basic aqueous solution may be selected fromamong an aqueous ammonia solution, an aqueous sodium hydroxide solution,an aqueous lithium hydroxide solution, and hydrazine, preferably anaqueous ammonia solution. Although sodium hydroxide and lithiumhydroxide can cause precipitation of an impurity having low solubilityand deterioration in yield, sodium hydroxide and lithium hydroxide donot affect purity. The basic aqueous solution may be used in an amountof 3 moles to 10 moles with respect to 1 mole of the polyol compound.Here, reaction may be performed at a temperature of 20° C. to 100° C.,preferably 40° C. to 70° C. Although reaction can occur without asolvent, the solvent may be selected from among toluene, methylenechloride, xylene, chlorobenzene, and dichlorobenzene, preferablytoluene.

Generally, a polyurethane-based eyeglass lens is produced by heat-curinga uniform optical composition in a glass mold, followed by releasing amolded product from the glass mold, in which the uniform opticalcomposition is prepared by mixing polyisocyanateas a polyurethanecompound having a liquid phase (I) with a polyol or polythiol compoundhaving a liquid phase (II), followed by degassing.

As the compound having a liquid phase (I), the polyiso(thio)cyanatecompound may be selected from any compounds having at least oneiso(thio)cyanate group without being limited to a particular compound.Examples of the polyiso(thio)cyanate compound may be classified into analiphatic polyisocyanate, an alicyclic polyisocyanate, and an aromaticpolyisocyanate, and specific examples thereof are disclosed in priordocuments and thus are not specifically recited herein.

Among these polyisocyanate compounds, m-xylylene diisocyanate(XDI),2,5(6)-bis(isocyanate methyl)-bicyclo[2,2,1]heptane(NBDI),1,6-hexamethylenediisocyanate(HDI), isophoronediisocyanate(IPDI), anddicyclohexylmethanediisocyanate(HMDI) are preferably used, and biuretderivatives of isocyanate and trimer derivatives (for example,polyisocyanurate) of isocyanate may also be used.

The biuret type isocyanate may be easily prepared using 1,2-ethylenediisocyanate, 1,3-propylene diisocyanate, 1,4-butylene diisocyanate,1,6-hexamethylene diisocyanate, 1,7-heptamethylene diisocyanate,1,8-octamethylene diisocyanate, 1,9-nonamethylene diisocyanate, or1,10-decamethylene diisocyanate as a raw material. In addition, theprepared biuret type isocyanate may be used after purification or as amixture of raw monomer materials. Alternatively, the biuret typeisocyanate may be obtained from commercially available products such asDesmodur N100 (Bayer Co., Ltd.) or Tolonate HDB LV (Perstop Co., Ltd.).In addition, the trimer type isocyanate may be easily prepared using thesame raw materials as the raw materials for the biuret type isocyanateor may be obtained from commercially available products, such asTolonate HDT LV (Vencorex Co., Ltd.), and the like.

In addition, as the compound having a liquid phase (II), the polythiolmay further include additional polythiol compounds as well as thepolythiol compound prepared by the method according to the presentinvention. The additional polythiol compound may be selected from anycompounds having at least one thiol group or mixtures thereof, withoutlimitation. Particularly, the polythiol compound may include at leastone selected from the group consisting of:

1,2-bis(2-mercaptoethylthio)-3-mercaptopropane,trimethylolpropanetris(mercaptopropionate),pentaerythritoltetrakis(mercaptopropionate),2,3-bis(2-mercaptoethylthio)propane-1-thiol,2-(2-mercaptoethylthio)-3-[2-(3-mercapto-2-(2-mercaptoethylthio)-propylthio]ethylthio-propane-1-thiol,2-(2-mercaptoethylthio)-3-{2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio}-propane-1-thiol,trimethylolpropanetris(mercaptopropionate,trimethylolethanetris(mercaptopropionate),glyceroltris(mercaptopropionate),trimethylolchlorotris(mercaptopropionate),trimethylolpropanetris(mercaptoacetate),trimethylolethanetris(mercaptoacetate),pentaerythritoltetrakis(mercaptopropionate),pentaerythritoltetrakis(mercaptoacetate),[1,4]dithiane-2-yl-methanethiol,2-(2-mercapto-ethylsulfanyl)-propane-1,3-dithiol,2-([1,4]dithiane-2-ylmethylsulfanyl)-ethanethiol,3-(3-mercapto-propionylsulfanyl)-propionic acid2-hydroxylmethyl-3-(3-mercapto-propionyloxy)-2-(3-mercapto-propionyloxymethyl)-propylester,3-(3-mercapto-propionylsulfanyl)-propionic acid3-(3-mercapto-propionyloxy)-2,2-bis-(3-mercapto-propionyloxymethyl)-propylester,(5-mercaptomethyl-[1,4]dithiane-2-yl)-methanethiol,1,3-bis(2-mercaptoethylthio)propane-2-thiol(GST),(3,6,10,13-tetrathiapentadecane-1,8,15-trithiol)(SET),2-(2-mercaptoethylthio)propane-1,3-dithiol(GMT),4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (DMDDU), andmixtures thereof.

Among these polythiol compounds,1,3-bis(2-mercaptoethylthio)propane-2-thiol (GST),(3,6,10,13-tetrathiapentadecane-1,8,15-trithiol)(SET), andpentaerythritoltetrakis(mercaptopropionate) (PEMP) are preferably used.More preferably, a mixture of1,3-bis(2-mercaptoethylthio)propane-2-thiol(GST) andpentaerythritoltetrakis(mercaptopropionate) (PEMP) is used.

A mole ratio (NCO/SH) of a functional group (—NCO) of the polyisocyanateused as the compound having a liquid phase (I) to a functional group(—SH) of the polythiol used as the compound having a liquid phase (II)may be in the range of 0.5 to 1.5. Preferably, the mole ratio rangesfrom 0.9 to 1.1, more preferably, 1.0, to secure further improvedproperties of the optical lens.

When HDI biuret, HDI trimer(HDI derivative), HDI, and IPDI are usedtogether as the polyisocyanate, these compounds may be used in a weightratio of 30 to 40:20 to 30:30 to 40. Although the polythiol prepared bythe method according to the present invention may be used alone, typicalpolythiols, such as GST, PEMP, and the like, may be suitably mixedtherewith in order to achieve desired refractivity and impactresistance, as needed.

In preparation of the polymerizable composition according to the presentinvention, the composition may include various additives in order toobtain essential optical properties for lenses, such as transparency,refractivity, specific gravity, impact resistance, heat resistance, andviscosity of a resin prepared from the polymerizable composition, asneeded. The composition may further include a UV or near-IR absorbent,dyes, a light stabilizer, an antioxidant, and the like, as additives.Furthermore, the composition may further include an epoxy compoundcopolymerizable with a urethane resin composition, a thio-epoxycompound, a vinyl group or unsaturated group-containing compound, or ametal compound.

Further, in order to regulate the reaction rate, the composition mayfurther include a catalyst. The catalyst may be, for example, a catalystfor urethane reaction and may be selected from tin compounds, such asdibutyltindilaurate, dibutyltin dichloride, dimethyltin dichloride,tetramethyl diacetoxydistannoxane, tetraethyl diacetoxydistannoxane,tetrapropyl diacetoxy distannoxane, and tetrabutyl diacetoxydistannoxane, or amine compounds including tertiary amine. These may beused alone or as a mixture thereof. The catalyst may be present in anamount of 0.001 wt % to 1 wt % based on the total weight of monomers ofthe composition. Within this range, the composition can have goodproperties in terms of polymerizability, pot life, transparency, variousoptical properties or light resistance of a resin produced therefrom.

In addition, the resin composition for optical lenses according to thepresent invention may further include a bluing agent for correction ofan initial color of a lens. Examples of the bluing agent may include anorganic dye, an organic pigment, an inorganic pigment, and the like.Such an organic dye may be present in an amount of 0.1 to 50,000 ppm,preferably 0.5 to 10,000 ppm, in the resin composition for opticallenses to enable color correction of a lens together with addition of aUV absorbent, an optical resin and monomers.

The resin composition for optical lenses according to the presentinvention may further include a typical release agent and a typicalpolymerization initiator. The release agent may be selected from thegroup consisting of a fluorine-based non-ionic surfactant, asilicon-based non-ionic surfactant, an alkyl quaternary ammonium salt,and mixtures thereof. Preferably, the release agent is phosphoric acidester. In addition, the polymerization initiator may be selected fromamong amine-based and tin-based compounds. These may be used alone or asa mixture thereof.

A polyurethane lens according to the present invention is evaluated asto properties of eyeglass lenses. For evaluation of the properties, (1)index of refraction (n_(D) ²⁰) and Abbe's number (νd), (2) heatresistance (Tg), and (3) thermal analysis were evaluated by thefollowing methods.

(1) Index of refraction (n_(D) ²⁰) and Abbe's number (νd): The index ofrefraction and Abbe's number were measured at 20° C. using an ABBErefractometer (1T model of ATAGO Co., Ltd.).

(2) Heat resistance: Glass transition temperature (Tg) of a specimen wasmeasured using a heat analyzer DSC N-650 (SCINCO Co., Ltd.) and definedas heat resistance.

(3) Thermal analysis: Thermal analysis of a lens was directly performedon a plastic lens sample using D1 (SINCO Co., Ltd.).

(Representative Method of Manufacturing Optical Lens)

Monomers constituting the polyisocyanate and monomers constituting thepolythiol are mixed and stirred in a particular ratio. Then,predetermined amounts of a release agent, a UV absorbent, an organicdye, and a curing catalyst are added to the prepared mixture. Then, aprepared polyurethane optical resin composition is subjected todegassing for a predetermined period of time and injected into a glassmold assembled by an adhesive tape.

Thereafter, the glass mold containing the mixture is placed in aforcible circulation type oven. In the oven, the mixture is polymerizedby maintaining the mixture at room temperature for a predeterminedperiod, gradually elevating the temperature of the mixture, andmaintaining the mixture at the elevated temperature, followed by coolingthe mixture.

After completion of polymerization, a resulting product is separatedfrom the mold, thereby providing a urethane optical lens. Then, the lensis subjected to annealing at 120° C. for 1 hour and 40 minutes. Afterannealing, a non-treated lens is released from the glass mold, therebyproviding an optical lens having a thickness of 1.2 mm. The preparedoptical lens is processed to a diameter of 80 mm and sequentiallysubjected to ultrasonic washing in an alkali aqueous washing liquid,annealing at 120° C. for 2 hours, and coating by dipping in asilicone-based hard liquid, followed by heat drying.

The optical lens according to the present invention may be subjected tophysical and chemical treatments, such as surface grinding, antistatictreatment, hard coat treatment, non-reflection coat treatment, dyeingtreatment, and photochromic treatment for the purpose of impartingantireflective properties, high hardness, abrasive resistance, chemicalresistance, anti-fog properties, fashionability and the like, as needed.

EXAMPLE

Hereinafter, the present invention will be described in more detail withpreparative examples and examples. However, it should be understood thatthese preparative examples and examples are provided for illustrationonly and the present invention is not limited thereto.

A preparation starting material can be easily produced from propyleneoxide. 1-mercaptopropan-2-ol was obtained from products of Aldrich GmbHand 2-mercaptopropan-1-ol was obtained from products of Bocsic Co., Ltd.

Preparative Examples 1 to 9 of Polyol Preparative Example 1:1-chloro-3-((2-hydroxypropyl)thio)propane-2-ol [Compound 1]

500 g (5.43 moles) of 1-mercaptopropan-2-ol (Aldrich Co., Ltd.) and 54.9g of triethylamine were placed in a reactor. Then, with the temperatureof the reactor set to 15° C., 502 g (5.43 moles) of epichlorohydrin wasslowly added dropwise to the solution, thereby preparing 1,002 g ofCompound 1. According to NMR-data of FIG. 1, the compound has thefollowing chemical properties: ¹H-NMR (D₂O), δ_(ppm)=1.26 (3H, d, CH3),2.66 to 2.90 (4H, m, CH₂—S), 3.70 to 3.82 (2H, m, CH₂—Cl).

Preparative Example 2: 2-((3-chloro-2-hydroxypropyl)thio)propane-1-ol[Compound 2]

500 g (5.43 moles) of 1-mercaptopropan-2-ol and 55.0 g of triethylaminewere placed in a reactor. Then, with the temperature of the reactor setto 15° C., 502 g (5.43 moles) of epichlorohydrin was slowly addeddropwise to the solution, thereby preparing 1,002 g of Compound 2.According to NMR-data, the compound has the following chemicalproperties: ¹H-NMR (D2O), δ_(ppm)=1.25 (3H, d, CH3), 2.66 to 2.90 (4H,m, CH₂—S), 3.65 to 3.82 (2H, m, CH₂—Cl).

Preparative Example 3: 3-((2-hydroxypropyl)thio)propane-1,2-diol[Compound 3]

After 200 g of H₂O was supplied to a reactor, 105 g (1.03 moles) oftriethylamine was added thereto and the temperature of the reactor wasset to 25° C. while stirring the mixture in the reactor. 200 g (2.17moles) of 1-mercaptopropan-2-ol was added to the reactor, and, with thetemperature of the reactor set to 20° C., 169 g (2.28 moles) of glycidolwas added dropwise to the solution for about 1 hour and additionallystirred, thereby preparing 353.6 g of Compound 3. According to NMR-dataof FIG. 2, the compound has the following chemical properties: ¹H-NMR(D2O), δ_(ppm)=1.22 (6H, d, CH3), 2.63 to 2.81 (4H, m, CH₂—S), 3.47 to4.1 (4H, m, CH—O, CH₂—O), 4.80 (3H, s, OH).

Preparative Example 4: 1,3-bis[(2-hydroxypropyl)thio]-2-propane-2-ol[Compound 4]

After 87.5 g of H₂O was supplied to a reactor, 87.3 g (1.09 moles) ofsodium hydroxide was added thereto and the temperature of the reactorwas set to 25° C. while stirring the mixture in the reactor. 199.2 g(2.16 moles) of 1-mercaptopropan-2-ol was added to the reactor, which inturn was set to a temperature of 20° C. Thereafter, 100 g (1.08 mole) ofepichlorohydrin was added dropwise to the reactor for about 1 hour,followed by stirring for 1 hour, thereby preparing 259.4 g of Compound4. According to NMR-data of FIG. 3, the compound has the followingchemical properties: ¹H-NMR (D2O), δ_(ppm)=1.24 (6H, d, CH3), 2.63 to2.87 (8H, m, CH₂—S), 3.97 (3H, m, CH—O), 4.80 (3H, s, OH).

Preparative Example 5:bis[3-((2-hydroxypropyl)thio)-2-hydroxypropyl]sulfide [Compound 5]

With a reactor maintained at 40° C., 890 g (2.71 moles) of an aqueoussodium sulfate solution was slowly added dropwise to Compound 1 preparedin Preparative Example 1, followed by stirring for 1 hour, therebypreparing 896.6 g of Compound 5. According to NMR-data of FIG. 4, thecompound has the following chemical properties: ¹H-NMR (D₂O),δ_(ppm)=1.29 (6H, d, CH₃), 2.67 to 2.95 (8H, m, CH₂—S), 4.02 (4H, m,CH—O)

Preparative Example 6:bis[3-((1-hydroxy-propane-2-yl)thio)-2-hydroxypropyl]sulfide [Compound6]

With a reactor maintained at 40° C., 890 g (2.71 moles) of an aqueoussodium sulfate solution was slowly added dropwise to Compound 2 preparedin Preparative Example 2, followed by stirring for 1 hour, therebypreparing 892.3 g of Compound 6. According to NMR-data, the compound hasthe following chemical properties: ¹H-NMR (D₂O), δ_(ppm)=1.25 (6H, d,CH₃), 2.65 to 2.95 (8H, m, CH₂—S), 4.07 (4H, m, CH—O).

Preparative Example 7: 1-((3-chloro-2-hydroxypropyl)thio)botane-2ol[Compound 7]

500 g (4.71 moles) of 1-mercaptobutane-2-ol and 47.6 g of triethylaminewere placed in a reactor. Then, with the temperature of the reactor setto 15° C., 435.7 g (4.71 moles) of epichlorohydrin was slowly addeddropwise to the solution, thereby preparing 935.6 g of Compound 7.According to NMR-data of FIG. 5, the compound has the following chemicalproperties: ¹H-NMR (MeOD), δ_(ppm)=0.94 (3H, t, CH₃), 1.4 to 1.65 (2H,m, CH₂), 2.58 to 2.82 (4H, m, CH₂—S—CH₂), 3.58 to 3.92 (3H, m,CH—O/CH₂—Cl), 4.82 (2H, s, OH)

Preparative Example 8:bis[3-((2-hydroxybutyl)thio)-2-hydroxypropyl]sulfide [Compound 8]

With a reactor maintained at 40° C., 782 g (2.35 moles) of an aqueoussodium sulfate solution was slowly added dropwise to Compound 7 preparedin Preparative Example 7, followed by stirring for 1 hour, therebypreparing 844.2 g of Compound 8. According to NMR-data of FIG. 6, thecompound has the following chemical properties.

¹H-NMR (MeOD), δ_(ppm)=0.96 (6H, t, CH₃), 1.41 to 1.68 (4H, m, CH₂),2.58 to 2.89 (12H, m, CH₂—S), 3.61 (2H, m, CH—O), 3.88 (2H, m, CH—O),4.81 (4H, S, OH)

Preparative Example 9: 1,3-bis[(2-hydroxybutyl)thio]propane-2-ol[Compound 9]

After 87.5 g of H₂O was supplied to a reactor, 87.3 g (1.09 moles) ofsodium hydroxide was added thereto and the temperature of the reactorwas set to 25° C. while stirring the mixture in the reactor. 229.5 g(2.16 moles) of 1-mercaptobutane-2-olwas added to the reactor, which inturn was set to 20° C. Thereafter, 100 g (1.08 moles) of epichlorohydrinwas added dropwise to the reactor for about 1 hour, followed by stirringfor 1 hour, thereby preparing 290.1 g of Compound 9. According toNMR-data of FIG. 7, the compound has the following chemical properties.

¹H-NMR (MeOD), δ_(ppm)=0.95 (6H, t, CH₃), 1.40 to 1.68 (4H, m, CH₂),2.58 to 2.89 (12H, m, CH₂—S), 3.61 (2H, m, CH—O), 3.88 (2H, m, CH—O),4.91 (3H, s, OH)

Examples 10 to 12 of Polythiol Preparative Example 10: (Preparation of2-((1-mercaptopropan-2-yl)thio)propane-1,3-dithiol) [Compounds 10-1 to10-4] (GPT)

In a reactor, 904 g (8.68 moles) of 35% HCl aqueous solution was addedto Compound 3 prepared in Preparative Example 3, followed by adding 512g (6.72 moles) of thiourea. Then, the components were stirred at 110° C.for 12 to 24 hours under temperature elevation and reflux conditions.Thereafter, with the mixture cooled to room temperature, 600 mL oftoluene was added to the mixture and 663.68 g (9.76 moles) of 25%aqueous ammonia was slowly added to the mixture, followed by hydrolysisat 65° C. for 3 hours. An organic layer obtained by the above processwas cooled to room temperature, followed by sequentially washing with200 mL of 36% hydrochloric acid solution, 200 mL of water, 200 mL of adiluted aqueous ammonia, and 200 mL of water three times. The organiclayer was separated and subjected to vacuum evaporation, therebypreparing 300 g of a colorless and transparent polythiol compound.

As a result of analysis of the prepared compound under the sameconditions as those of high performance liquid chromatography ofreparative Example 11, the prepared compound consisted of about 60% toabout 70% of Compound 10-1 as a main reaction product and 40% or less ofCompounds 10-2 to 10-4, which are isomers of Compound 10-1. Referring toFIG. 8 showing NMR-data of a mixture of Compounds 10-1 to 10-4,Compounds 10-1 to 10-4 have the following chemical properties: ¹H-NMR(CDCl3), δ_(ppm)=1.25 to 1.42 (3H, m, CH₃), 1.68 to 2.0 (3H, m, SH),2.59 to 3.33 (8H, m, CH₂—S, CH—S); Index of refraction (n_(D) ²⁰): 1.618

Preparative Example 11: (Preparation of3-((1-mercaptopropan-2-yl)thio)-2((1-mercaptopropan-2-yl)thio)propane-1-thiol)[Compounds 11-1 to 11-4] (MPT)

In a reactor, 394 g (3.78 moles) of 35% HCl aqueous solution was added(at 30° C. or less) to Compound 4 prepared in Preparative Example 4,followed by adding 250.9 g (3.30 moles) of thiourea. Then, thecomponents were stirred at 110° C. for 12 to 24 hours under temperatureelevation and reflux conditions. Then, with the mixture cooled to roomtemperature, 550 mL of toluene was added to the mixture and 282.7 g(4.32 moles) of 25% aqueous ammonia was slowly added to the mixture,followed by hydrolysis at 65° C. for 3 hours. The temperature of anorganic layer obtained by the above process was cooled to roomtemperature, followed by sequentially washing with 57 mL of 36%hydrochloric acid solution and 400 mL of water. The organic layer wasseparated and subjected to vacuum evaporation, thereby preparing 290 gof a colorless and transparent polythiol compound.

The compound prepared in Preparative Example 11 also has four isomers.Thus, as a result of analysis of the prepared compound under the sameconditions as those of high performance liquid chromatography describedbelow, Compound 11-1 (main reaction product) was present in an amount ofabout 84% to about 88% and each of Compounds 11-2 to 11-4, which areisomers of Compound 11-1, was present in an amount of 8% or less.According to NMR-data FIG. 9, Compounds 11-1 to 11-4 have the followingchemical properties: ¹H-NMR (CDCl3), δ_(ppm)=1.35 to 1.42 (6H, m, CH3),1.70 to 2.28 (3H, m, SH), 2.59 to 3.16 (11H, m, CH₂—S, CH—S); CH—S);Index of refraction (n_(D) ²⁰): 1.601

The conditions for high performance liquid chromatography (HLPC) forconfirmation of isomers were as follows:

Conditions for high performance liquid chromatography (HLPC)

Column: Wathers ODS (Φ 6 mm×250 mm)

Moving phase: acetonitrile/10 mmol—Aqueous sodium acetate solution

90/10 (vol/vol)→0/100 (vol/vol) (change for 20 minutes)

Column temperature: 25° C.

Flux: 1.0 ml/min

Detector: UV detector, wavelength: 215 nm

Measurement solution concentration: 100 mg of a specimen in 10 mlacetonitrile

Injection amount: 10 μL

Peak area ratio of isomer

A ratio of an integrated area of each isomer to the sum of total areasof Compound 11-1 produced as the main reaction product of the polythiolcompound and Compounds 11-2, 11-3 and 11-4 produced as isomers thereofwas calculated. As a result, Compound 11-2 was present in a ratio of0.03 to 0.04, Compound 11-3 was present in a ratio of 0.04 to 0.05, andCompound 11-4 was present in a ratio of 0.03 to 0.08.

Preparative Example 12:3,3′-thiobis(2-((1-mercaptopropan-2-yl)thio)-1-propanethiol) [Compounds12-1 to 12-10] (BPT)

In a reactor, 2,239.6 g (13.5 moles) of 49% hydrobromic acid and 836.3 g(10.9 moles) of thiourea were added to Compound 5 prepared inPreparative Example 5, followed by heating at 105° C. for 6 hours whilestirring the mixture. Then, the mixture was cooled to room temperature,and 2,000 g of toluene and 1,700 g of water were added to the mixture,which in turn was slowly heated to 70° C. Then, 1,596 g (9 moles) of 25%aqueous ammonia was slowly added dropwise to the mixture. A water layerwas removed from the mixture and an organic layer was cooled to roomtemperature and washed with 100 g of 36% hydrochloric acid and 1,000 gof distilled water, followed by vacuum distillation, thereby preparing1,070 g of Compounds 12-1 to 12-10.

As a result of analysis of the prepared compounds under the sameconditions as those of high performance liquid chromatography ofPreparative Example 11, Compound 12-1 was present as a main reactionproduct in an amount of about 63% to about 70% and each of Compounds12-2 and 12-3, which are isomers of Compound 12-1, was present in anamount of 14% or less. Other isomers were present in a total amount ofabout 2% to about 8%. Referring to FIG. 10 showing NMR-data of a mixtureof Compounds 12-1 to 12-10, Compound 12-1 has the following chemicalproperties:

1H-NMR (CDCl₃), δ_(ppm)=1.36 to 1.4 (6H, m, CH₃), 1.65 to 2.32 (4H, m,SH), 2.6 to 3.18 (16H, m, CH₂—S, CH—S); index of refraction (n_(D) ²⁰):1.621

Preparative Example 13:2,2′-((thiobis(1-mercaptopropan-3,2-diyl))bis(sulfondiyl))bis(butane-1-thiol)[Compounds 13-1 to 13-10] (BBT)

In a reactor, 1,225.2 g (11.8 moles) of 35% HCl aqueous solution wasadded (at 30° C. or less) to Compound 8 prepared in Preparative Example8, followed by adding 727.6 g (9.56 moles) of thiourea. Then, thecomponents were stirred at 110° C. for 12 to 24 hours under temperatureelevation and reflux conditions. Thereafter, with the mixture cooled toroom temperature, 2,000 mL of toluene was added to the mixture and 846.6g (12.95 moles) of 25% aqueous ammonia was slowly added to the mixture,followed by hydrolysis at 65° C. for 3 hours. An organic layer obtainedby the above process was cooled to room temperature, followed bysequentially washing with 1000 mL of 36% hydrochloric acid solution and100 mL of water. The organic layer was separated and subjected to vacuumevaporation, thereby preparing 1,104 g of a colorless and transparentpolythiol compound as Compound 15.

As a result of analysis of the prepared compound under the sameconditions as those of high performance liquid chromatography ofPreparative Example 11, Compound 13-1 was present as a main reactionproduct in an amount of about 60% to about 70% and each of Compounds13-2 and 13-3, which are isomers of Compound 13-1, was present in anamount of 15% or less. Other isomers were present in a total amount ofabout 2% to about 3%. According to NMR-data of FIG. 11, the compound hasthe following chemical properties.

1H-NMR (CDCl3), δ_(ppm)=1.11 (6H, m, CH₃), 1.65 (4H, m, SH), 1.75 to1.91 (4H, m, CH₂), 2.62 to 3.15 (16H, m, CH—S/CH₂—S); index ofrefraction (n_(D) ²⁰): 1.602

Preparative Example 14:3-((1-mercaptobutane-2-yl)thio)-2-((1-mercaptobutane-2-yl)thio)propane-1-thiol[Compounds 14-1 to 14-4] (MPT)

In a reactor, 394 g (3.78 moles) of 35% HCl aqueous solution was added(at 30° C. or less) to Compound 9 prepared in Preparative Example 9,followed by adding 250.9 g (3.30 moles) of thiourea. Then, thecomponents were stirred at 110° C. for 12 to 24 hours under temperatureelevation and reflux conditions. Thereafter, with the mixture cooled toroom temperature, 550 mL of toluene was added to the mixture and 282.7 g(4.32 moles) of 25% aqueous ammonia was slowly added to the mixture,followed by hydrolysis at 65° C. for 3 hours. An organic layer obtainedby the above process was cooled to room temperature, followed bysequentially washing with 57 mL of 36% hydrochloric acid solution and400 mL of water. The organic layer was separated and subjected to vacuumevaporation, thereby preparing 318.2 g of colorless and transparentpolythiol compounds as Compounds 14-1 to 14-4.

As a result of analysis of the prepared compounds under the sameconditions as those of high performance liquid chromatography ofPreparative Example 11, Compound 14-1 was present as a main reactionproduct in an amount of about 80% to about 95% and each of Compounds14-2 to 14-4, which are isomers of Compound 14-1, was present in anamount of 5% or less. According to NMR-data of FIG. 12, the compound hasthe following chemical properties.

1H-NMR (CDCl3), δ_(ppm)=1.11 (6H, t, CH₃), 1.62 (3H, m, SH), 1.75 to1.89 (4H, m, CH₂), 2.62 to 3.0 (9H, m, CH—S/CH₂—S); Index of refraction(n_(D) ²⁰): 1.599

As described above, the compound according to the present invention iscomposed of a mixture of a polythiol main product containing a primarythiol having a mercaptomethyl group and polythiol isomers containing asecondary thiol. Thus, according to the present invention, it can beunderstood that the polythiol compound of Compound 10(GPT) theoreticallyconsists of a main compound and 4 isomers, and the polythiol compound ofeach of Compound 11(MPT) and Compound 14(MBT) theoretically consists ofa main compound and 4 isomers excluding isomers having the same atomarrangement among 10 isomers thereof. On the other hand, the polythiolcompound of each of Compound 12(BPT) and Compound 13(BBT) has 10 isomersexcluding isomers having the same atom arrangement among 16 isomersthereof.

On the other hand, as mentioned in Background Art, Patent Document 4discloses substitution of an isothiouronium salt at a carbon locationhaving a hydroxyl group in preparation of an isothiouronium saltcompound through reaction of a sulfur-containing polyol with thioureaunder acid conditions. However, it is believed that rearrangementallowing selective introduction of thiourea through steric hindrancealso occurs in an activation process in which an episulfonium salthaving a sulfur atom is generated. Then, the isothiouronium saltcompound having a modified main chain structure is hydrolyzed, therebyproducing a compound in which a mercaptomethyl group is introduced intoa main chain structure of a polythiol compound.

In summary, in the process of preparing the polythiol compound accordingto the present invention, it is not believed that only the compoundhaving an isothiouronium salt substituted at the carbon location havinga hydroxyl group is generated without rearrangement through sterichindrance, as disclosed in Patent Document 4. Therefore, it is believedthat a secondary thiol compound having a thiol group at a carbonlocation where a hydroxyl group of a polyol intermediate compound isplaced cannot be prepared as a main reaction product in PreparativeExample (1) of the prior patent document.

Next, optical lenses were manufactured using the polythiol compoundsaccording to the present invention together with a polyisocyanatetypically used in the art and compared with optical lenses ofComparative Examples 1 to 4. In particular, the lenses were prepared toevaluate properties of lenses according to each polythiol in LensPreparation Examples 1 to 13.

1) According to the representative method of manufacturing an opticallens described above, each of the polythiol compounds prepared inPreparative Examples, a polyisocyanate compound, and additives (releaseagent and polymerization initiator) were mixed in amounts as listed inTables 1 to 4 and formed into an optical lens through polymerization ina mold, followed by evaluation of index of refraction, Abbe's number,heat resistance, and the like.

Here, the release agent was a Zelec UN (Dupont). The polymerizationinitiator was selected from among dibutyltin dichloride and tincompounds. In addition, UV absorbents, bluing agents (organic dyes,organic pigments, inorganic pigments, and the like), and the like wereused, as needed. In the following examples, the content of eachcomponent is represented in terms of wt % with reference to gram (g).

2) Multilayer splitting was observed by leaving prepared lenses underconditions of 75% RH (relative humidity) and an inner temperature of 80°C. for 1 hour. Splitting was evaluated by the following standards, thatis, A: no splitting, B: 1 or more split marks, and C: significantsplitting.

3) For evaluation of dyeing properties, each of plastic lenses preparedusing compositions, for example, XDI/BPT, XDI/BET, XDI/MPT, XDI/GST, andthe like, listed in each table, was dipped in a dyeing bath filled witha mixture of 500 g of distilled water and 17.5 g of ONS black at atemperature of 85° C. to 95° C. for 5 minutes. Then, the degree ofdyeing of each lens was evaluated.

4) In Examples 1 to 13 and Tables 1 to 4, BPT, MPT, GPT, BBT and MBTrefer to the compounds prepared in Preparative Examples 10, 11, 12, 14and 15, respectively, and acronyms of these compounds are shown in theaforementioned tables. In addition, isocyanate compounds such as XDI,Biuret, HDI, NBDI, IPDI, and HMDI used together with well-knownpolythiol compounds such as GST and BET(3,3′-thiobis[2-[(2-mercaptoethyl)thio]-1-propanethiol) are alsomentioned above and thus detailed description thereof will be omitted.

In Lens Preparation Examples 1 and 2, lenses were prepared using XDI asan isocyanate and MPT and BPT as the polythiol compounds according tothe present invention, instead of GST and BET, respectively. Then, theprepared lenses were compared with commercially available lenses ofComparative Examples 1 and 2.

In Lens Preparation Examples 3 and 4, lenses were prepared using aBiuret compound as an isocyanate, and MPT and BPT instead of GST andBET, respectively. Then, the prepared lenses were compared withcommercially available lenses of Comparative Examples 3 and 4. In LensPreparation Examples 5 to 10, lenses were prepared using variousisocyanates (NBDI, IPDI, and HMDI) instead of XDI. Table 3 showsimprovement of functionality such as heat resistance and dyeingproperties due to increase in glass transition temperature Tg. Inaddition, lenses were prepared using XDI and novel polythiol compounds,such as GPT, MBT, and BBT, as the polythiol compound according to thepresent invention. Table 4 shows the index of refraction, Abbe's number,heat resistance, dyeing properties and functionality of these lenses.

Lens Preparation Examples 1 and 2

The following table shows the index of refraction, Abbe's number, heatresistance, and multilayer splitting of each of the lenses according tothe present invention and the lenses of comparative examples.

TABLE 1 Ex. Ex. Ex. Ex. Ex. Ex. Comp. Comp. 1-1 1-2 1-3 2-1 2-2 2-3 Ex.1 Ex. 2 Monomers XDI 10 10 10 9.76 9.76 9.76 11 11 (g) MPT 10.2 10.210.2 BPT 10.91 10.91 10.91 GST 9.595 BET 9.87 Release agent 0.024 0.0240.024 0.024 0.024 0.024 0.024 0.024 Polymerization 0.004 0.004 0.0040.004 0.004 0.004 0.004 0.004 initiator Lens n_(D) ²⁰ 1.641 1.641 1.6401.650 1.650 1.650 1.657 1.655 properties Abbe's 33.2 33.5 33.3 32.3 32.532.4 31 31 number Heat 97.3 96.0 97.6 103.5 103.0 103.1 85.0 100.0resistance (° C.) Dyeing ⊚ ⊚ ⊚ ◯ ◯ ◯ ◯ ◯ property Multilayer A A A A A AB A splitting 1) Comparative Example 1: A commercially available productof Mitsui Chemical Co., Ltd., index of refraction(n_(D) ²⁰): 1.657, andheat resistance: 85° C. 2) Comparative Example 2: A commerciallyavailable product of Mitsui Chemical Co., Ltd., index ofrefraction(n_(D) ²⁰): 1.655, and heat resistance: 100° C. 3) Dyeingproperties: ⊚: Excellent, O: Good, Δ: Normal, X: Poor 4) Splitting: A:no splitting, B: one or more splitting marks; C: significant splitting

The lens of Comparative Example 1 is mainly composed of XDI as anisocyanate and GST as a polythiol compound, and has a glass transitiontemperature Tg of about 85° C. and a disadvantage of low heatresistance. It is known in the art that this lens suffers from splittingof multilayer coating in a high temperature condition, such as a saunabath and the like. On the other hand, this lens has good dyeingproperties in order to improve functionality, such as UV or sunlightshielding. In order to solve the problem of low heat resistance, MitsuiChemical Co., Ltd. developed a novel product (Comparative Example 2). Alens of Comparative Example 2 is mainly composed of XDI and BET insteadof GST as a polythiol compound. However, it is known in the art thatthis lens fails to satisfy dyeing properties for improvement infunctionality, despite improvement in heat resistance.

In Table 1, the lens of Comparative Example 1 suffering from splittingof the multilayer coating is compared with the lenses of Examples 1-1 to1-3 according to the present invention. Referring to Table 1, the lensesof the examples had similar indices of refraction to the lens ofComparative Example 1 and 12.3° C. higher heat resistance than the lensof Comparative Example 1, and improved Abbe's number, particularlydyeing properties. Upon multilayer coating after manufacture of thelens, the lens of Comparative Example 1 suffered from damage to themultilayer coating under conditions of 75% RH and 80° C., whereas thelens of Example 1 maintained an original shape thereof without sufferingfrom damage to the multilayer coating under the same conditions.Therefore, it could be confirmed that MPT corresponding to the polythiolcompound according to the present invention had better properties thanGST used in the art.

In addition, the lenses of Examples 2-1 to 2-3 had slightly betterrefractivity and heat resistance than the lens of Comparative Example 2and exhibited good dyeing properties. Therefore, it could be confirmedthat BPT corresponding to the polythiol compound according to thepresent invention had similar or better properties to or than BET usedin the art.

Lens Preparation Examples 3 and 4

Lenses were prepared by the same method as the above examples exceptthat hexamethylene diisocyanate biuret was used as an isocyanate insteadof XDI and the amounts of components for compounds were changed aslisted in Table 1.

TABLE 2 Com- Comparative parative Example 3 Example 4 Example 3 Example4 Monomers Biuret 13 12.88 13.46 15 (g) MPT 6.99 BPT 7.11 GST 6.54 BET8.61 Release agent 0.024 0.024 0.024 0.024 Polymerization 0.0125 0.01250.0125 0.0125 initiator Lens n_(D)

1.577 1.579 1.596 1.589 properties Abbe's 40.1 34.8 39.3 35.8 numberHeat 84.7 96.7 75.8 86.6 resistance (° C.) Dyeing ⊚ ⊚ ⊚ ⊚ propertyMultilayer B A C B splitting

indicates data missing or illegible when filed

In Table 2, the lenses of Examples 3 and 4 were prepared using the sameisocyanate, that is, Biuret, as the lenses of Comparative Examples 3 and4. As compared with the lens of Comparative Example 1, the lens ofExample 3 improved in heat resistance by about 10° C. or more andexhibited very good dyeing properties, despite a lower index ofrefraction. Upon multilayer coating after manufacture of the lens, thelens of Comparative Example 3 suffered from damage to the multilayercoating under conditions of 75% RH and 80° C. However, the lens ofExample 3 maintained an original shape thereof without suffering fromdamage to the multilayer coating under the same conditions. Therefore,it could be confirmed that MPT corresponding to the polythiol compoundaccording to the present invention had better properties than GST usedin the art.

As compared with the lens of Comparative Example 4, the lens of Example4 improved in heat resistance by about 10° C. or more and exhibited verygood dyeing properties (since the lens of Example 4 had good dyeingproperties, both lenses had similar dyeing properties), despite a lowerindex of refraction. Therefore, it could be confirmed that BPTcorresponding to the polythiol compound according to the presentinvention had similar or better properties to or than BET used in theart.

Lens Preparation Examples 5 to 10

Lenses were prepared by the same method as the above examples exceptthat NBDI was used as an isocyanate and the amounts of components forcompounds were changed as listed in Table 1.

TABLE 3 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10Monomers NBDI 10.34 10.21 (g) IPDI 11 10.59 HMDI 12 11.41 MPT 9.65 9.528.79 BPT 10.4 10.41 8.58 Release agent 0.024 0.024 0.024 0.024 0.0240.024 Polymerization 0.0125 0.0125 0.0125 0.0125 0.0125 0.0125 initiatorLens n_(D) ²⁰ 1.604 1.614 1.581 1.589 1.583 1.590 properties Abbe's 37.743 41.3 35.9 45.3 38.6 number Heat 124.7 133.3 106.1 123.1 99.0 111.6resistance (° C.) Dyeing ◯ ◯ ◯ ◯ ⊚ ◯ property Multilayer A A A A A Asplitting

Table 3 shows the contents of NBDI, IPDI, and HMDI among non-yellowingisocyanates applicable to transparent optical lenses. Here, theproperties of lenses prepared by the same method as in the aboveexamples were compared according to MPT and BPT. As an isocyanatecompound used in preparation of lenses of Examples 5 and 6, NBDIprovided an index of refraction of about 1.604 to 1.614 and acombination of NBDI-BPT provided a very high Abbe's number of about 43.The combination of NBDI-BPT provided a very high heat resistance of133.3° C. and a combination of NBDI-MPT also provided a very high heatresistance of 124.7° C. and thus could be suitably used for improvementin heat resistance. These lenses also exhibited good properties in termsof dyeing properties and suppression of multilayer splitting.

Lenses of Examples 7 and 8 were prepared using IPDI. The lens of Example7 prepared using a combination of IPDI-MPT had a heat resistance ofabout 106.1° C. and exhibited good dyeing properties, which are relatedto heat resistance. The lens of Example 8 had a heat resistance of about123.1° C. and thus achieved significant improvement in heat resistance.

Lenses of Examples 9 and 10 were prepared using HMDI. The lens ofExample 9 prepared using a combination of HMDI-MPT had a very highAbbe's number of about 45 and very good dyeing properties.

Lens Preparation Examples 11 to 13

The properties of lenses prepared using various isocyanates wereevaluated in order to determined usability of the lenses as transparentlenses. Here, the lenses were evaluated as to the index of refraction,Abbe's number, heat resistance, dyeing properties, and the like. Inaddition, the lenses were prepared using XDI as an isocyanate and GPT,MBT or BBT having an elongated chain structure, such as butylene oxide,as the polythiol instead of MPT or BPT, which are derivatives ofpropylene oxide, to determine applicability of GPT, MBT and BBT togetherwith XDI.

TABLE 4 Example Example Example 11 12 13 Monomers (g) XDI 11.36 10.40510.13 GPT 10.03 MBT 13.5 BBT 13.24 Release agent 0.024 0.024 0.024Polymerization initiator 0.004 0.004 0.004 Lens n_(D) ²⁰ 1.649 1.6321.638 properties Abbe's number 27.5 30 32.5 Heat resistance 110.07 78.594.2 (° C.) Dyeing property ◯ ⊚ ⊚ Multilayer A C A splitting

In Table 4, the lenses of Examples 11, 12, and 13 had an index ofrefraction of 1.63 or more, despite lower indices of refraction thanthose of the lenses of Comparative Examples 1 and 2 shown in Table 1,thereby showing that the compound according to the present invention canbe applied to materials requiring relatively high refractivity andultrahigh refractivity. In addition, the lenses prepared in theseexamples exhibited improvement in heat resistance, dyeing properties,and suppression of multilayer splitting.

For the lens of Example 11, such differences in effect resulted from theuse of GPT, which is a polythiol prepared using a polyol of Compound 3prepared using 1-mercaptopropan-2-ol derived from propylene oxide andglydicol instead of epichlorohydrin, instead of GST used in preparationof the lens of Comparative Example 1 in Table 1. According to thepresent invention, when the volume of the polythiol increases throughsubstitution of a methyl group or an ethyl group to a side chain of thepolythiol, the glass transition temperature of the lens is maintained at110° C., thereby improving heat resistance while providing good dyeingproperties for improvement in functionality.

The lenses of Examples 12 and 13 were prepared using a polyol and apolythiol, which were prepared from butylene oxide instead of propyleneoxide. The lens of Example 12 prepared using MBT instead of GSTexhibited a high index of refraction and good dyeing properties, despitean unexpectedly low glass transition temperature Tg. The lens of Example13 prepared using BBT instead of BET had a high index of refraction of1.638 and a glass transition temperature Tg of 94.2° C., providingsuitable heat resistance for coloration. From these results, it could beseen that the polyol and the polythiol compounds according to thepresent invention have applicability to novel polythiol or urethaneoptical materials.

The properties of the optical lenses of Examples 1 to 13 prepared usingvarious polythiol compounds according to the present invention werecompared with the properties of the lenses of Comparative Examples 1 to4. As a result, it could be seen that the lenses according to thepresent invention generally had improved heat resistance to suppressmultilayer splitting in a high temperature condition, such as a saunabath and the like. In addition, it could be seen that the lensesaccording to the present invention were changed to exhibit the mostsuitable heat resistance through a magnification method. Further, itcould be seen that the lenses according to the present invention hadimprovement in dyeing properties and Abbe's number to reduce fatigue onthe eye even when a user wears the lens for a long period of time.Accordingly, it can be seen that a lens having improvement in heatresistance, dyeing properties, Abbe's number and suppressing multilayersplitting as compared with a lens in the art can be manufactured usingthe novel polythiol according to the present invention.

As a result, when the polythiol compound according to the presentinvention is used as a main component of a polymerizable composition forurethane-based optical materials, it is possible to manufacture anoptical lens having good heat resistance. In particular, a conventionalpolythiol compound starts from ‘2-mercapto ethanol’, whereas thepolythiol compound according to the present invention starts from‘2-mercaptopropanol’, ‘1-mercaptopropan-2-ol’, or‘1-mercaptobutane-2-ol’. Thus, it is believed that the polythiolcompound according to the present invention enables preparation ofinexpensive urethane-based resins for optical materials and thus can bebroadly applied to materials for optical lenses.

As a starting material of a conventional polythiol compound, 2-mercaptoethanol is prepared from ethylene oxide and hydrogen sulfide, whereas1-mercaptopropan-2-ol of the polythiol compound according to the presentinvention may be prepared from propylene oxide and hydrogen sulfide.Ethylene oxide used in the art has a gaseous phase at room temperatureand has problems of difficulty in handling and high possibility ofexplosion at room temperature, whereas propylene oxide used in thepresent invention has a liquid phase at room temperature and allows easyhandling and good stability at room temperature. Accordingly, it isbelieved that the polythiol compound according to the present inventionenables economically inexpensive preparation of 1-mercaptopropan-2-oland thus has better economic feasibility than the conventional polythiolcompound.

A polyurethane resin for optical materials according to the presentinvention is not limited to lenses. For example, it is possible toimpart a polarizing function (a function of minimizing reflection on asurface of a non-metallic material allowing transmission of light onlyat a certain angle) and a dimming function (a function of enablingautomatic control of illumination intensity based on surroundingenvironments and space usage) to a polyurethane resin substrate.Furthermore, it is possible to impart an eyesight correction function tothe polyurethane resin substrate for eyeglass lenses.

On the other hand, the polyurethane resin substrate is applied to aneyeglass lens as an optical body in the above description. However, itshould be understood that the optical body according to the presentinvention may also be applied as a construction material to large-areawindows, such as sliding windows, single or double hung windows,side-hinged windows, and the like, which are used in buildings and thelike, as needed. In order to apply the polyurethane resin compositionaccording to the present invention to such large-area windows, thepolyurethane resin composition may further include additivescorresponding to additional functions. For example, the resincomposition may be formed in a shape corresponding to a window frame,cured in a glass mold having various shapes, and released from the moldto be used in a building.

1-23. (canceled)
 24. A polyol or polythiol compound or an isomerthereof, the polyol or polythiol compound having at least threefunctional groups and represented by Formula (a) or (b):

(where Y is an oxygen atom or a sulfur atom; Ra is a lower alkyl group;i) for the polyol, Rb is —CH₂CH(OH)CH₂F, —CH₂CH(OH)CH₂Cl,—CH₂CH(OH)CH₂Br, —CH₂CH(OH)CH₂I,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₃,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₃)CH₂OH, —CH₂CH(OH)CH₂SCH₂CH(OH)CH₃,—CH₂CH(OH)CH₂SCH(CH₃)CH₂OH, —CH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃,—CH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃, or—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH; ii) for the polythiol, Rb is—CH(CH₂SH)CH₂SH, —CH₂CH(CH₂SH)SCH(CH₃)CH₂SH, —CH₂CH(CH₂SH)SCH₂CH(CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₃)CH₂SH, —CH(CH₂SH)CH₂SCH₂CH(CH₃)SH,—CH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH, —CH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, —CH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, or—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH).
 25. The polyol compoundaccording to claim 24, as represented by Formula (a) or (b), wherein Yis an oxygen atom; Ra is a methyl or ethyl group; and Rb is onesubstituent selected from the group consisting of the followingsubstituents: —CH₂CH(OH)CH₂F, —CH₂CH(OH)CH₂Cl, —CH₂CH(OH)CH₂Br,—CH₂CH(OH)CH₂I, —CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₃,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₃)CH₂OH, —CH₂CH(OH)CH₂SCH₂CH(OH)CH₃,—CH₂CH(OH)CH₂SCH(CH₃)CH₂OH, —CH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃,—CH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH,—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH₂CH(OH)CH₂CH₃, and—CH₂CH(OH)CH₂SCH₂CH(OH)CH₂SCH(CH₂CH₃)CH₂OH.
 26. The polythiol compoundaccording to claim 24, as represented by Formula (a) or (b), wherein Yis a sulfur atom; Ra is a methyl or ethyl group; and Rb is onesubstituent selected from the group consisting of the followingsubstituents: —CH(CH₂SH)CH₂SH, —CH₂CH(CH₂SH)SCH(CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₃)SH, —CH(CH₂SH)CH₂SCH(CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₃)SH, —CH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH, —CH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH, —CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₃)SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₃)SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH,—CH(CH₂SH)CH₂SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH(CH₂CH₃)CH₂SH,—CH₂CH(CH₂SH)SCH₂CH(CH₂SH)SCH₂CH(CH₂CH₃)SH,—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH(CH₂CH₃)CH₂SH, and—CH₂CH(CH₂SH)SCH(CH₂SH)CH₂SCH₂CH(CH₂CH₃)SH.
 27. A poly(thio)urethaneresin composition comprising the polythiol compound having at leastthree functional groups according to claim 24 and a polyisocyanate. 28.A poly(thio)urethane resin composition comprising the polythiol compoundhaving at least three functional groups according to claim 26 and apolyisocyanate.
 29. The poly(thio)urethane resin composition accordingto claim 27, wherein a mole ratio (NCO/SH) of a functional group (—NCO)of the polyisocyanate to a functional group (—SH) of the polythiolcompound is in the range of 0.8 to 1.3.
 30. The poly(thio)urethane resincomposition according to claim 28, wherein a mole ratio (NCO/SH) of afunctional group (—NCO) of the polyisocyanate to a functional group(—SH) of the polythiol compound is in the range of 0.8 to 1.3.
 31. Thepoly(thio)urethane resin composition according to claim 27, thepoly(thio)urethane resin composition is used as a plastic optical body.32. The poly(thio)urethane resin composition according to claim 28, thepoly(thio)urethane resin composition is used as a plastic optical body.33. The poly(thio)urethane resin composition according to claim 29, thepoly(thio)urethane resin composition is used as a plastic optical body.34. The poly(thio)urethane resin composition according to claim 30, thepoly(thio)urethane resin composition is used as a plastic optical body.35. The poly(thio)urethane-based plastic optical body according to claim33, wherein the plastic optical body is optical glasses or an opticallens.
 36. The poly(thio)urethane-based plastic optical body according toclaim 34, wherein the plastic optical body is optical glasses or anoptical lens.